KR20080036553A - Method for making an epoxide starting with a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent - Google Patents

Abstract

The invention concerns a method for making an epoxide which consists in subjecting in a reaction medium resulting from the reaction between a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, and a chlorinating agent, the reaction medium containing at least 10 mg of chlorohydrin per kg of reaction medium, to a subsequent chemical reaction without any intermediate treatment.

Description

METHOD FOR MAKING AN EPOXIDE STARTING WITH A POLYHYDROXYLATED ALIPHATIC HYDROCARBON AND A CHLORINATING AGENT}

This patent application is filed on May 20, 2005, with patent application FR 05.05120 and patent application EP 05104321.4, and US provisional patent application 60/734659, 60/734627, 60/734657, 60, filed November 8, 2005. / 734658, 60/734635, 60/734634, 60/734637 and 60/734636 are the basis of a priority claim, the contents of all of which are incorporated herein by reference.

The present invention relates to a method of preparing an epoxide. Epoxides are an important raw material for preparing other compounds.

For example, ethylene oxide is used to prepare ethylene glycol, di- and polyethylene glycols, mono-, di- and triethanolamines, and the like (K. Weissermel and HJ Arpe in Industrial Organic Chemistry, Third Completely Revised Edition, VCH). , 1997, page 149). Propylene oxide is an important intermediate in the production of propylene 1,2-glycol, dipropylene glycol, ethers of propylene glycol, isopropylamine, etc. (K. Weissermel and HJ Arpe in Industrial Organic Chemistry, Third Completely Revised Edition, VCH , 1997, page 275). Epichlorohydrin is an important raw material for the production of glycerol, epoxy resins, synthetic elastomers, glycidyl ethers, polyamide resins, etc. (Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, Vol. A9, p. 539 ] Reference).

In the industrial preparation of propylene oxide, the most commonly used techniques are hypochlorination of propylene with monochloropropanol and dehydrochlorination of monochloropropanol with propylene oxide using an alkaline aqueous solution. It includes.

In the industrial preparation of epichlorohydrin, the most commonly used techniques are the steps of hot free radical substitution chlorination of propylene with allyl chloride, hypochlorination of the allyl chloride thus synthesized with dichloropropanol, and alkaline aqueous solution Dehydrochlorination of dichloropropanol with epichlorohydrin. Other techniques used on a smaller scale include catalytic acetoxylation of propylene with allyl acetate, hydrolyzing allyl acetate with allyl alcohol, catalytic chlorination of allyl alcohol with dichloropropanol, and epidiol dichloropropanol. Alkaline dechlorination with chlorohydrin. Other techniques that are not yet used industrially can be contemplated, including the direct catalytic catalytic oxidation of allyl chloride to epichlorohydrin with hydrogen peroxide, or chlorinated glycerol with dichloropropanol, followed by dichloromethane. Alkaline dehydrogenation of the propanol with epichlorohydrin is included.

Application of SOLVAY SA WO 2005/054167 describes a method for preparing dichloropropanol by reacting glycerol and hydrogen chloride in the presence of an organic acid as a catalyst. In this process, dichloropropanol is separated from other reaction products, hydrogen chloride and organic acids, and the dichloropropanol undergoes dehydrochlorination to give a reaction product containing epichlorohydrin. Dehydrochlorination can be carried out in the presence of a basic preparation, in particular an aqueous solution of the basic preparation. If the organic acid forms an azeotrope with water, or if its relative volatility is significant in the ternary water / dichloropropanol / hydrogen chloride mixture, the separation of the organic acid is not good, in which case the dichloropropanol also forms an ether with the organic acid, making it an ether. It becomes contaminated.

It is an object of the present invention to provide a process for the preparation of epoxides which does not exhibit this disadvantage.

Accordingly, the present invention is a reaction medium produced by reacting polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons, or mixtures thereof with chlorinating agents, wherein the reaction contains at least 10 g of chlorohydrin per kg of reaction medium. Provided are methods for the preparation of epoxides in which the media is subsequently chemically reacted without intermediate treatment.

The subsequent chemical reaction is preferably a dehydrochlorination reaction.

The dehydrochlorination reaction is preferably carried out by adding a basic compound to the reaction medium.

Thus, the present invention more specifically,

(a) Reacting polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof with chlorinating agents and organic acids, esters of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons, water, chlorine Forming a chlorohydrin and chlorohydrin ester in a reaction medium containing at least 10 g of chlorohydrin per kg of reaction medium, as a reaction medium containing an agent and an organic acid,

(b) at least one fraction of the reaction medium obtained in step (a), wherein the fraction having the same composition as the reaction medium obtained in step (a) is subjected to at least one treatment in a step subsequent to step (a), and

(c) adding the basic compound to one or more steps subsequent to step (a) to react with chlorohydrin, chlorohydrin esters, chlorinating agents and organic acids to form epoxides and salts

It provides a method for producing an epoxide comprising a.

It has been found that the step of separating the organic acid and its derivatives is not essential because the epoxide can be prepared in excellent yield by reacting a mixture containing chlorohydrin, chlorinating agent and organic acid with the basic compound. Surprisingly, the formation of salts resulting from neutralization of chlorinating agents and organic acids with basic compounds and hydrolysis of esters formed between chlorohydrin and organic acids, even when a significant amount of organic acid is present in the reaction (c) step with the basic compound Even if it does not interfere with the manufacturing reaction of an epoxide. A significant advantage of this reaction is that there is no need to separate the chlorinating agent and organic acid used in the preparation of chlorohydrin.

The term "epoxide" is used herein to describe compounds containing at least one oxygen crosslinked on a carbon-carbon bond. Generally speaking, the carbon atoms of the carbon-carbon bond are adjacent and the present compound may contain atoms other than carbon atoms and oxygen atoms, for example hydrogen atoms and halogens. Preferred epoxides are ethylene oxide, propylene oxide, glycidol, epichlorohydrin and mixtures of two or more thereof.

The term "olefin" is used herein to describe compounds containing one or more carbon-carbon double bonds. Generally speaking, the present compounds may contain atoms other than carbon atoms, for example hydrogen atoms and halogens. Preferred olefins are ethylene, propylene, allyl chloride and mixtures of two or more thereof.

The term "polyhydroxylated aliphatic hydrocarbon" refers to a hydrocarbon containing two or more hydroxyl groups attached to two different saturated carbon atoms. Polyhydroxylated aliphatic hydrocarbons may contain, but are not limited to, 2 to 60 carbon atoms.

Each carbon of a polyhydroxylated aliphatic hydrocarbon having hydroxyl functional groups (OH) cannot have more than one OH group and must have sp3 hybridization. Carbon atoms with OH groups must be primary, secondary or tertiary. The polyhydroxylated aliphatic hydrocarbons used in the present invention should contain at least two sp3-hybridized carbon atoms with OH groups. Polyhydroxylated aliphatic hydrocarbons comprise vicinal diols (1,2-diols) or vicinal triols (1,2) comprising these repeating units in a higher, vicinal or contiguous order , 3-triol), including any hydrocarbon. The definition of polyhydroxylated aliphatic hydrocarbons also includes, for example, one or more 1,3-, 1,4-, 1,5- and 1,6-diol functional groups. The polyhydroxylated aliphatic hydrocarbon may also be a polymer such as polyvinyl alcohol. Gemal diols, for example, are excluded from this group of polyhydroxylated aliphatic hydrocarbons.

Polyhydroxylated aliphatic hydrocarbons may include aromatic moieties or heteroatoms (eg, heteroatoms including halogen, sulfur, phosphorus, nitrogen, oxygen, silicon and boron types), and mixtures thereof.

Polyhydroxylated aliphatic hydrocarbons that can be used in the present invention are, for example, 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1-chloro- 2,3-propanediol (chloropropanediol), 2-chloro-1,3-propanediol (chloropropanediol), 1,4-butanediol, 1,5-pentanediol, cyclohexanediol, 1,2-butanediol , 1,2-cyclohexanedimethanol, 1,2,3-propanetriol (also known as "glycerol" or "glycerine"), and mixtures thereof. Preferably, the polyhydroxylated aliphatic hydrocarbons used in the present invention are for example 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, chloropropanediol and 1,2,3- Propanetriol and mixtures of two or more thereof. More preferably, the polyhydroxylated aliphatic hydrocarbons used in the present invention are for example 1,2-ethanediol, 1,2-propanediol, chloropropanediol and 1,2,3-propanetriol, and these Mixtures of two or more of them. Most preferred is 1,2,3-propanetriol or glycerol.

Esters of polyhydroxylated aliphatic hydrocarbons may be present in the polyhydroxylated aliphatic hydrocarbons and / or prepared in the chlorohydrin preparation process and / or prepared prior to the chlorohydrin preparation process. Examples of esters of polyhydroxylated aliphatic hydrocarbons include ethylene glycol monoacetate, propanediol monoacetate, glycerol monoacetate, glycerol monostearate, glycerol diacetate and mixtures thereof.

The term "chlorohydrin" is used herein to describe compounds containing one or more chlorine atoms and one or more hydroxyl groups attached to different saturated carbon atoms. Chlorohydrins containing two or more hydroxyl groups are also polyhydroxylated aliphatic hydrocarbons. Thus, the starting material and the reaction product may each be chlorohydrin. In that case, the "product" chlorohydrin is more chlorinated than the starting chlorohydrin, ie it has more chlorine atoms and fewer hydroxyl groups than the starting chlorohydrin. Preferred chlorohydrins are chloroethanol, chloropropanol, chloropropanediol, dichloropropanol and mixtures of two or more thereof. Dichloropropanol is particularly preferred. More particularly preferred chlorohydrins are 2-chloroethanol, 1-chloropropan-2-ol, 2-chloropropan-1-ol, 1-chloropropane-2,3-diol, 2-chloropropane-1,3- Diol, 1,3-dichloropropan-2-ol, 2,3-dichloropropan-1-ol and mixtures of two or more thereof.

In the process according to the invention the polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons, or mixtures thereof can be obtained starting from fossil raw materials or renewable raw materials, preferably starting from renewable raw materials. Can be.

Fossil raw material means a material obtained from the treatment of petrochemical natural resources such as petroleum, natural gas and coal. Among these materials, organic compounds containing 2 and 3 carbon atoms are preferred. When chlorohydrin is diclopropanol or chloropropanediol, allyl chloride, allyl alcohol and "synthetic" glycerol are particularly preferred. "Synthetic" glycerol generally means glycerol obtained from petrochemical resources. When chlorohydrin is chloroethanol, ethylene and "synthetic" ethylene glycol are particularly preferred. "Synthetic" ethylene glycol generally means ethylene glycol obtained from petrochemical resources. When chlorohydrin is monochloropropanol, propylene and "synthetic" propylene glycol are particularly preferred. "Synthetic" propylene glycol generally means propylene glycol obtained from petrochemical resources.

Renewable raw material means a material obtained from the treatment of renewable natural resources. Of these materials, "natural" ethylene glycol, "natural" propylene glycol and "natural" glycerol are preferred. "Natural" ethylene glycol, propylene glycol and glycerol are obtained, for example, by conversion of sugars by thermochemical processes, which are described in "Industrial Bioproducts: Today and Tomorrow", Energetics, Incorporated for the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Office of the Biomass Program, July 2003, pages 49, 52 to 56. One such method is the catalytic hydrogenolysis of sorbitol, for example obtained by thermochemical conversion of glucose. Another method is the catalytic hydrogenolysis of xylitol, for example obtained by hydrogenation of xylose. Xylose can be obtained, for example, by hydrolysis of hemicellulose present in corn fiber. "Natural glycerol" or "glycerols obtained from renewable raw materials" is especially generally used for the production of biodiesel or other glycerol obtained during the conversion of animal or vegetable oils, or animal fats or plant fats, such as saponification, transesterification or hydrolysis reactions. Glycerol obtained during the mean.

Among the oils that can be used in the natural glycerol production process mentioned, all conventional oils, for example palm oil, palm kernel oil, copra oil, babass oil, old or new (low-erucic acid) colza oil, sunflower oil, corn Oil, castor oil and cotton oil, peanut oil, soybean oil, soybean oil, linseed oil and crambe oil, and sunflower or colza plants obtained, for example, by genetic modification or hybridization. All oils obtained from can be mentioned.

It is also possible to use waste cooking oil, various animal oils such as fish oil, tallow, lard and squaring grease.

Among the oils used, mention may be made, for example, of oils partially modified by polymerization or oligomerization of stand oils of linseed oil and sunflower oil, and blown vegetable oils.

Particularly suitable glycerol can be obtained during the conversion of animal fats. Other particularly suitable glycerol can be obtained during the production of biodiesel. A third very suitable glycerol can be obtained during the conversion of animal or vegetable oils, or animal fats or plant fats by transesterification in the presence of heterogeneous catalysts, as described in documents FR 2752242, FR # 2869612 and FR 2869613. More specifically, the heterogeneous catalyst is selected from mixed oxides of aluminum and zinc, mixed oxides of zinc and titanium, mixed oxides of zinc, titanium and aluminum, mixed oxides of bismuth and aluminum, and the heterogeneous catalyst is in the form of a fixed bed. Used as This latter method may be a biodiesel manufacturing method.

Chloroethanol can be obtained starting from these raw materials via any method. Preference is given to hypochlorination of ethylene and to chlorination of "synthetic" and / or "natural" ethylene glycol. Particular preference is given to methods of chlorination of "synthetic" and / or "natural" ethylene glycol.

Chloropropanol can be obtained starting from this source by any method. Preference is given to hypochlorination of propylene and to chlorination of "synthetic" and / or "natural" propylene glycol. Particular preference is given to methods of chlorination of "synthetic" and / or "natural" propylene glycol.

Chloropropanediol can be obtained starting from this source by any method. Preference is given to the method of chlorination of "synthetic" and / or "natural" glycols.

Dichloropropanol can be obtained starting from this source by any method. Preferred methods are hypochlorination of allyl chloride, chlorination of allyl alcohol and chlorination of "synthetic" and / or "natural" glycerol. Particular preference is given to methods of chlorination of "synthetic" and / or "natural" glycerol.

In the epoxide production process according to the invention, it is preferred to prepare at least one fraction of chlorohydrin by chlorinating the polyhydroxylated aliphatic hydrocarbon. The polyhydroxylated aliphatic hydrocarbon may be "synthetic" or "natural" in the meaning defined above.

In the production process according to the invention, when the epoxide is epichlorohydrin, the "natural" glycerol, i.e. biodiesel production process or animal oil or vegetable oil, or animal fat or plant fat conversion process (saponification, transesterification and Preference is given to a glycerol obtained from the hydrolysis reaction). Particular preference is given to glycerol obtained from the transesterification of fats or oils of vegetable or animal origin (performed in the presence of a heterogeneous catalyst). In the process for the preparation of epoxides according to the invention, the polyhydroxylated aliphatic hydrocarbons are filed under the name Solvay SA on the same date as the present application, the contents of which are incorporated herein by reference to convert the "polyhydroxylated aliphatic hydrocarbons As described in a patent application entitled "Method for Making Hydrin".

A process for producing chlorohydrin, wherein a polyhydroxylated aliphatic hydrocarbon, an ester of polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, having a total metal content in elemental form of at least 0.1 µg / kg and up to 1000 µg / kg is reacted with a chlorinating agent Particular mention is made.

In the process for the preparation of the epoxide according to the invention, for example, according to the method described in the application WO 2005/054167 of Solvay SA, the content of which is incorporated herein by reference, polyhydroxylated aliphatic hydrocarbon, polyhydroxylation It is possible to use chlorohydrins obtained by starting from esters of aliphatic hydrocarbons or mixtures thereof and reacting them with chlorinating agents.

In the process for producing epoxides according to the invention, the polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof can be crude or purified products, which are described in Solvay SA application WO 2005/054167, 2nd line 8th thru | or 2nd line 4th page.

In the epoxide production process according to the invention, the polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons and mixtures thereof may have an alkali metal and / or alkaline earth metal content of 5 g / kg or less. Filed under the same name as Solvay SA in the present application, the content may be as described in a patent application entitled "Method for Converting Polyhydroxylated Aliphatic Hydrocarbons to Produce Chlorohydrin", herein incorporated by reference. .

In the process according to the invention, the alkali metal and / or alkaline earth metal content of the polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is 5 g / kg or less, often 1 g / kg or less, more In particular, it is 0.5 g / kg or less, in some cases 0.01 g / kg or less. The alkali metal and / or alkaline earth metal content of glycerol is generally at least 0.1 μg / kg.

In the epoxide production process according to the invention, the alkali metals are generally lithium, sodium, potassium and cesium, often sodium and potassium, and often sodium.

In the method for producing chlorohydrin according to the present invention, the lithium content of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is generally at most 1 g / kg, often at most 0.1 g / kg, more Especially 2 mg / kg or less. This content is generally at least 0.1 µg / kg.

In the process according to the invention, the sodium content of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is generally at most 1 g / kg, often at most 0.1 g / kg, more particularly at 2 gmg / kg. kg or less. This content is generally at least 0.1 µg / kg.

In the process according to the invention, the potassium content of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is generally at most 1 g / kg, often at most 0.1 g / kg, more particularly at 2 gmg / kg. kg or less. This content is generally at least 0.1 µg / kg.

In the process according to the invention, the rubidium content of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is generally at most 1 g / kg, often at most 0.1 g / kg, more particularly at 2 gmg / kg. kg or less. This content is generally at least 0.1 µg / kg.

In the process according to the invention, the cesium content of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is generally at most 1 g / kg, often at most 0.1 g / kg, more particularly at 2 gmg / kg. kg or less. This content is generally at least 0.1 µg / kg.

In the process according to the invention, alkaline earth metal elements are generally magnesium, calcium, strontium and barium, often magnesium and calcium, often calcium.

In the process according to the invention, the magnesium content of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is generally at most 1 g / kg, often at most 0.1 g / kg, more in particular at 2 mg / g. kg or less. This content is generally at least 0.1 µg / kg.

In the process according to the invention, the calcium content of the polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is generally at most 1 g / kg, often at most 0.1 g / kg, more in particular at 2 gmg / kg. kg or less. This content is generally at least 0.1 µg / kg.

In the process according to the invention, the strontium content of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is generally at most 1 g / kg, often at most 0.1 g / kg, more in particular at 2 gmg / kg. kg or less. This content is generally at least 0.1 µg / kg.

In the process according to the invention, the barium content of the polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is generally at most 1 g / kg, often at most 0.1 g / kg, more in particular at 2 gmg / kg. kg or less. This content is generally at least 0.1 µg / kg.

In the process according to the invention, alkali metals and / or alkaline earth metals are generally present in salt form, often in the form of chlorides, sulfates and mixtures thereof. Sodium chloride is the most common.

In the epoxide production method according to the invention, the chlorinating agent of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is described in Solvay SA application WO 2005/054167, page 4, lines 30 to Hydrogen chloride and / or hydrochloric acid as described in line 6, line 2.

Particular mention is made of chlorinating agents which may be aqueous hydrochloric acid or preferably anhydrous hydrogen chloride. Hydrogen chloride is obtained from the method of pyrolyzing organic chlorine compounds, for example from the production of vinyl chloride, from the method of producing 4,4-methylenediphenyl diisocyanate (MDI) or toluene diisocyanate (TDI), the metal pickling process ) Or from reactions of inorganic acids such as sulfuric acid or phosphoric acid with metal chlorides such as sodium chloride, potassium chloride or calcium chloride.

In an advantageous embodiment of the epoxide production process according to the invention, the chlorinating agent of a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture thereof is a gaseous hydrogen chloride or aqueous solution of hydrogen chloride or a combination of the two. .

In the process for preparing epoxides according to the invention, the chlorinating agents of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof are filed under the name Solvay SA on the same date as the present application, the contents of which are incorporated herein by reference. Allyl chloride production method and / or chloromethane production method and / or chlorination and as described in the application entitled "Method for preparing chlorohydrin by reacting a polyhydroxylated aliphatic hydrocarbon with a chlorinating agent" Or hydrochloric acid or hydrogen chloride, obtained from high temperature oxidation of the chlorine compound, or preferably anhydride.

From polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons, or mixtures thereof, and chlorinating agents (the chlorinating agents are nitrogen, oxygen, hydrogen, chlorine, organic hydrocarbon compounds, organic halogen compounds, organic oxygen compounds and metals) Mention is made in particular of the process for the preparation of chlorohydrin).

Particular mention is made of organic hydrocarbon compounds selected from saturated or unsaturated aliphatic and aromatic hydrocarbons and mixtures thereof.

Especially aromatic aliphatic hydrocarbons selected from acetylene, ethylene, propylene, butene, propadiene, methylacetylene and mixtures thereof, saturated aliphatic hydrocarbons selected from methane, ethane, propane, butane and mixtures thereof, and aromatic hydrocarbons which are benzene To mention.

Organic halogens which are organic chlorine compounds selected from chloromethane, chloroethane, chloropropane, chlorobutane, vinyl chloride, vinylidene chloride, monochloropropene, perchloroethylene, trichloroethylene, chlorobutadiene, chlorobenzene and mixtures thereof Particular mention is made of compounds.

Particular mention is made of organic halogen compounds which are organic fluorine compounds selected from fluoromethane, fluoroethane, vinyl fluoride, vinylidene fluoride and mixtures thereof.

Particular mention is made of organic oxygen compounds selected from alcohols, chloroalcohols, chloroethers and mixtures thereof.

Particular mention is made of metals selected from alkali metals, alkaline earth metals, iron, nickel, copper, lead, arsenic, cobalt, titanium, cadmium, antimony, mercury, zinc, selenium, aluminum, bismuth and mixtures thereof.

It is more particularly mentioned how the chlorinating agent is at least partly obtained in the process for producing allyl chloride and / or the process for producing chloromethane and / or the chlorination process and / or the process for chlorine compound oxidation at temperatures above 800 ° C.

In an advantageous embodiment of the epoxide production process according to the invention, the chlorinating agent of the polyhydroxylated aliphatic hydrocarbons, the esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof does not contain gaseous hydrogen chloride.

In the epoxide production method according to the invention, the chlorination reaction of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is described in Solvay SA application WO 2005/054167, page 6, lines 3 to 3 It can be carried out in the reactor described in line 23.

Reference is made in particular to plants which are made or covered with substances which are resistant to chlorinating agents, in particular hydrogen chloride, under the reaction conditions. Particular mention is made of plants made of enameled steel or tantalum.

In the epoxide production process according to the invention, the chlorination reaction of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is filed under the name Solvay SA on the same day as the present application, the content of which is herein As described in a patent application entitled "Method for Producing Chlorohydrin in a Corrosion-Resistant Device," which is incorporated by reference, it may be carried out in a device made or covered with a material resistant to chlorinating agents.

Reacting the polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof with a chlorinating agent containing hydrogen chloride and carrying out one or more other steps carried out in a device made or covered with a material resistant to the chlorinating agent Mention is made in particular of the process for the preparation of chlorohydrin, which comprises passing under conditions under which such steps are realized. Metallic materials such as enamel steel, gold and tantalum, and nonmetallic materials such as high density polyethylene, polypropylene, poly (vinylidene fluoride), polytetrafluoroethylene, perfluoroalkoxyalkanes and poly (perfluoro More particularly mention is made of graphite including ropropyl vinyl ether), polysulfone and polysulfide, and unimpregnated graphite.

In the epoxide production process according to the invention, the chlorination reaction of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is filed under the name Solvay SA on the same day as the present application, the content of which is herein As described in the application entitled “Continuous Method for Preparing Chlorohydrin”, which is incorporated by reference, can be carried out in a reaction medium.

The polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons, or mixtures thereof, may be prepared by the steady state composition of polyhydroxylated aliphatic hydrocarbons and polyhydroxylated aliphatic hydrocarbons (polyhydroxylated aliphatic hydrocarbons). Total content in moles of aliphatic hydrocarbon, greater than 1.1 mol% and up to 30 mol%, the percentage being based on the organic portion of the liquid reaction medium) of the chlorohydrin, which is reacted with the chlorinating agent and organic acid in a liquid reaction medium. Particular mention is made of continuous production processes.

The organic portion of the liquid reaction medium consists of all organic compounds of the liquid reaction medium, ie compounds in which the molecule contains one or more carbon atoms.

In the epoxide production method according to the invention, the chlorination reaction of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is described in Solvay SA application WO 2005/054167, page 6 line 28 to line It can be carried out in the presence of the catalyst described in line 5, line 8.

Particular mention is made of carboxylic acid based catalysts or carboxylic acid derivative based catalysts, especially adipic acid and adipic acid derivatives, having an atmospheric boiling point of at least 200 ° C.

In the epoxide production method according to the invention, the chlorination reaction of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is described in Solvay SA application WO 2005/054167, page 8, lines 6 to 8 It can be carried out during the residence time at the catalyst concentration, temperature and pressure described in page 10, line 10.

Particular mention is made of temperatures of at least 20 ° C. and at most 160 ° C., pressures of at least 0.3 kPa and at most 100 kPa, and residence times of at least 1 hour and at most 50 hours.

In the epoxide preparation method according to the invention, the chlorination reaction of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is described in Solvay SA application WO 2005/054167, page 11 line 12 to line 12 It may be carried out in the presence of the solvent described in line 36.

Organic solvents such as chlorinated organic solvents, alcohols, ketones, esters or ethers, non-aqueous solvents that are miscible with polyhydroxylated aliphatic hydrocarbons such as chloroethanol, chloropropanol, chloropropanediol, dichloropropanol, dioxane Particular mention is made of heavy reaction products such as phenols, cresols, and mixtures of chloropropanediol and dichloropropanol, or at least partially chlorinated and / or esterified oligomers of polyhydroxylated aliphatic hydrocarbons.

In the epoxide production process according to the invention, the chlorination reaction of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is filed under the name Solvay SA on the same day as the present application, the content of which is herein As described in the application entitled "Method for Making Chlorohydrin in Liquid Phase", which is incorporated by reference, it can be carried out in the presence of a liquid phase comprising a heavy compound that is not a polyhydroxylated aliphatic hydrocarbon.

Polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof are polyhydroxylated with a boiling point under absolute pressure of 1 Ibar at least 15 ° C. higher than the boiling point of chlorohydrin under absolute pressure of 1 bar. Particular mention is made of the process for the preparation of chlorohydrin, which is reacted with a chlorinating agent in the presence of a liquid phase comprising heavy compounds which are not aliphatic hydrocarbons.

In the epoxide production process according to the invention, the chlorination reaction of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is preferably carried out in a liquid reaction medium. The liquid reaction medium may be a single phase or a multiphase medium.

The liquid reaction medium consists of all dissolved or dispersed solid compounds, dissolved or dispersed liquid compounds and dissolved or dispersed gaseous compounds at the reaction temperature.

The reaction medium includes reactants, catalysts, solvents and also impurities present in the reactants, solvents and catalysts, reaction intermediates, products of reactions and by-products.

By reactants is meant polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons and chlorinating agents.

Among the impurities present in the polyhydroxylated aliphatic hydrocarbons are carboxylic acids, salts of carboxylic acids, fatty acid esters of polyhydroxylated aliphatic hydrocarbons, esters of alcohols used in transesterification reactions with fatty acids, and inorganic salts, for example Mention may be made of alkali metal or alkaline earth metal sulfates and chlorides.

When the polyhydroxylated aliphatic hydrocarbon is glycerol, the impurities in the glycerol may be carboxylic acids, salts of carboxylic acids, fatty acid esters, for example mono-, di- and triglycerides, esters of alcohols used for transesterification with fatty acids. And inorganic salts such as alkali or alkaline earth metal sulfates and chlorides.

Among the reaction intermediates, mention may be made of monochlorohydrins of polyhydroxylated aliphatic hydrocarbons and their esters and / or polyesters, esters of polyhydroxylated aliphatic hydrocarbons and / or esters of polyesters and polychlorohydrins. have.

When the chlorohydrin is dichloropropanol, the reaction intermediate comprises glycerol monochlorohydrin and its esters and / or polyesters, esters of glycerol and / or polyesters and esters of dichloropropanol.

Therefore, esters of polyhydroxylated aliphatic hydrocarbons may suitably be reactants, impurities of polyhydroxylated aliphatic hydrocarbons or reaction intermediates.

The reaction product means chlorohydrin and water. Water is formed during the chlorination reaction and / or, for example, application WO 2005/054167 to Solvay SA, lines 22 to 28 of page 2, lines 20 to 25 of page 3, and line 7 of page 5 Water may be introduced during the process via polyhydroxylated aliphatic hydrocarbons and / or chlorinating agents as described in rows 31-31 and page 14-19.

By-products can include, for example, partially chlorinated and / or esterified oligomers of polyhydroxylated aliphatic hydrocarbons.

If the polyhydroxylated aliphatic hydrocarbon is glycerol, the by-products may include, for example, partially chlorinated and / or esterified oligomers of glycerol.

The reaction intermediates and by-products can be formed in various process steps, for example, during step (a) and during the processing step following step (b).

Therefore, the liquid reaction medium is a polyhydroxylated aliphatic hydrocarbon, chlorinating agent, catalyst, solvent and also impurities present in the reactants, solvents and catalysts dispersed or dissolved in foam form, for example dissolved or solid salts, for example For example, reaction intermediates, reaction products and by-products.

Steps (a), (b) and (c) of the epoxide production method according to the invention can be carried out independently in a batch or continuous manner. Continuous mode is preferred. It is particularly preferred that all three stages are continuous.

In the production process according to the invention, the organic acid can be a product derived from a process for producing a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture thereof, or a product not derived from this process. In the latter case, the organic acid may be an organic acid used to catalyze the reaction of a polyhydroxylated aliphatic hydrocarbon with a chlorinating agent. The organic acid may also be a mixture of organic acids derived from a polyhydroxylated aliphatic hydrocarbon production method and organic acids not derived from a polyhydroxylated aliphatic hydrocarbon production method. Preference is given to using organic acids which are not obtained during the preparation of polyhydroxylated aliphatic hydrocarbons, which acids are used as reaction catalysts between polyhydroxylated aliphatic hydrocarbons and chlorinating agents. In particular, it is preferable to use acetic acid or adipic acid.

In the process according to the invention, the ester of the polyhydroxylated aliphatic hydrocarbon may be derived from the reaction between the polyhydroxylated aliphatic hydrocarbon and the organic acid before, during or within the stage following the reaction with the chlorinating agent. .

In the process according to the invention, the separation of chlorohydrin and other compounds from the reaction mixture is described in Solvay SA applications WO SA2005 / 054167, page 12, line 1 to page 16, line 35 and page 18, line 6 to It can be carried out according to the method described in line 13. These other compounds are those mentioned above and include unconsumed reactants, impurities present in the reactants, catalysts, solvents, reaction intermediates, water and reaction byproducts.

Particular mention is made of the separation by azeotropic distillation of the water / chlorohydrin / chlorinating mixture under the conditions of minimizing the loss of chlorinating agent, followed by the separation of chlorohydrin by decantation.

In the process for preparing epoxides according to the invention, the separation of chlorohydrin and other compounds from the reaction medium in the chlorination of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof may be carried out. It may be carried out according to a method of the type described in patent application EP 05104321.4, filed in the name of Solvay SA, which is incorporated herein by reference. Particular preference is given to a separation process comprising at least one separation operation for removing salts from the liquid phase.

Polyhydroxylated aliphatic hydrocarbons used, esters of polyhydroxylated aliphatic hydrocarbons, or mixtures thereof, include one or more solid or dissolved metal salts and include a separation operation to remove some of the metal salts. Particular mention is made of methods for producing chlorohydrins by reacting oxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof with chlorinating agents. The polyhydroxylated aliphatic hydrocarbons used, the esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof comprise at least one sodium chloride and / or potassium chloride and / or sodium sulfate and / or potassium sulfate and are used to remove some of the metal salts. More particularly refers to a process for preparing chlorohydrin by reacting a polyhydroxylated aliphatic hydrocarbon, an ester of polyhydroxylated aliphatic hydrocarbon, or a mixture thereof or a chlorinating agent, wherein the separation operation is a filtration operation. (a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof with a chlorinating agent in a reaction mixture, and (b) continuously or periodically containing at least water and chlorohydrin Remove the fraction of the reaction mixture, (c) introduce at least a portion of the fraction obtained in step (b) into the distillation step, and (d) adjust the reflux ratio of the distillation step by providing water to the distillation step, chlorohydrin Particular mention is also made of the process for the preparation of. (a) reacting polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof with hydrogen chloride in the reaction mixture, and (b) continuously or periodically containing at least water in chlorohydrin The fraction of the mixture is removed and (c) at least a portion of the fraction obtained in step (b) is introduced into the distillation stage, wherein the ratio between the hydrogen chloride concentration and the water concentration in the fraction introduced into the distillation stage is at distillation temperature and pressure. Very particular mention is made of the process for the preparation of chlorohydrin, which is less than the hydrogen chloride / water concentration ratio in the binary azeotropic hydrogen chloride / water composition.

In the epoxide production process according to the invention, the separation of chlorohydrin and other compounds from the reaction mixture in the chlorination of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is the same as in the present application. Filed under the name Solvay SA, the contents of which may be carried out according to the method described in the application entitled "Method for preparing chlorohydrin", which is incorporated herein by reference.

(a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture thereof with a chlorinating agent and an organic acid to obtain a mixture containing chlorohydrin and esters of chlorohydrin, (b) Subjecting at least a portion of the mixture obtained in step (a) to one or more treatments following step (a), and (c) adding polyhydroxylated aliphatic hydrocarbons to one or more steps following step (a), Reference is particularly made to a process for the preparation of chlorohydrin which comprises reacting an ester of chlorohydrin at a temperature of at least 20 ° C. to form at least partly an ester of polyhydroxylated aliphatic hydrocarbon. More particularly mention is a method wherein the polyhydroxylated aliphatic hydrocarbon is glycerol and the chlorohydrin is dichloropropanol.

In the epoxide production process according to the invention, the separation of chlorohydrin and other compounds from the reaction mixture in the chlorination of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is the same as in the present application. Filed under the name Solvay SA, the contents of which can be carried out according to the method described in the application entitled "Method for Making Chlorohydrin Starting from Polyhydroxylated Aliphatic Hydrocarbon", which is incorporated herein by reference.

Poly in the reactor fed one or more liquid streams containing less than 50% by weight of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof compared to the total weight of the liquid stream introduced into the reactor. Particular mention is made of the preparation of chlorohydrins by reacting chlorinating agents with esters of hydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or mixtures thereof. (a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof with a chlorinating agent to obtain at least one mixture containing chlorohydrin, water and a chlorinating agent, (b) Removing one or more fractions of the mixture formed in step (a), and (c) distilling and / or stripping the fractions removed in step (b), wherein polyhydroxylated aliphatic hydrocarbons are added to More particularly refers to a process comprising separating a mixture containing water and chlorohydrin from the fraction removed in step (b) and exhibiting a reduced chlorinating agent content compared to the fraction removed in step (b) .

In the epoxide production process according to the invention, the separation of chlorohydrin and other compounds in the reaction mixture from the chlorination of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is the same as in the present application. Filed in the name of Solvay SA, the contents of which may be performed according to the method described in the application entitled "Method for Converting Polyhydroxylated Aliphatic Hydrocarbons to Chlorohydrin", which is incorporated herein by reference.

(a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of polyhydroxylated aliphatic hydrocarbon or a mixture thereof with a chlorinating agent to obtain a mixture containing chlorohydrin, chlorohydrin ester and water, (b) step distilling and / or stripping one or more fractions of the mixture obtained in (a) to obtain a concentrated portion of water, chlorohydrin, and chlorohydrin esters, and (c) one of the portions obtained in step (b) A process for producing chlorohydrin comprising the step of separating and operating the above fractions in the presence of one or more additives to obtain a portion containing chlorohydrin and a chlorohydrin ester in which the chlorohydrin ester is concentrated and contains less than 40% by weight of water. To mention.

The separation operation is more particularly oblique separation.

In the process for preparing epoxides according to the invention, the separation and treatment of other compounds of the reaction medium from the chlorination of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof is the same as the Solvay SA name. It can be carried out according to the method described in the application entitled "Method for producing chlorohydrin by chlorination of polyhydroxylated aliphatic hydrocarbons" filed with. One preferred treatment consists in high temperature oxidation of the fraction of reaction by-products.

(a) reacting at least chlorohydrin and by-products by reacting polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof, chlorinating agents and organic acids with an alkali metal and / or alkaline earth metal content of 5 g / kg or less; Obtaining a mixture comprising (b) subjecting at least a portion of the mixture obtained in step (a) to one or more treatments in steps subsequent to step (a), and (c) subsequent to step (a) Mention is made in particular of the process for the preparation of chlorohydrin, wherein at least one of the steps comprises oxidizing at a temperature of at least 800 ° C. More particularly mention is made of the removal of a part of the mixture obtained in step (a), so that this part is oxidized at temperatures above 800 ° C. More particularly mention the process wherein the treatment of step (b) is a decantation or separation operation selected from filtration, centrifugation, extraction, washing, evaporation, stripping, distillation, adsorption or absorption operation or a combination of two or more thereof.

In the process according to the invention, when chlorohydrin is chloropropanol, chloropropanol is usually obtained in the form of a mixture of compounds comprising isomers of 1-chloropropan-2-ol and 2-chloropropan-1-ol. . This mixture generally contains more than 1% by weight, preferably more than 5% by weight, in particular more than 50% by weight, of two isomers. The mixture usually contains two isomers of less than 99.9% by weight, preferably less than 95% by weight and more particularly less than 90% by weight. Other components of the mixture may be compounds derived from the process for producing chloropropanol, for example residual reactants, reaction byproducts, solvents and especially water.

The mass ratio of the isomers 1-chloropropan-2-ol and 2-chloropropan-1-ol is usually at least 0.01, preferably at least 0.4. This ratio is usually 99 or less, preferably 25 or less.

In the process according to the invention, when the chlorohydrin is chloroethanol, the chloroethanol is generally obtained in the form of a mixture of compounds comprising the isomer 2-chloroethanol. This mixture generally contains more than 1% by weight, preferably more than 5% by weight, in particular more than 50% by weight. The mixture usually contains less than 99.9% by weight, preferably less than 95% by weight, more particularly less than 90% by weight. Other components of the mixture may be compounds derived from the process for preparing chloroethanol, for example residual reactants, reaction byproducts, solvents, and especially water.

In the process according to the invention, when the chlorohydrin is dichloropropanol, the dichloropropanol is in the form of a mixture of compounds comprising isomers of 1,3-dichloropropan-2-ol and 2,3-dichloropropan-1-ol It is common to get. This mixture generally contains more than 1% by weight, preferably more than 5% by weight, in particular more than 50% by weight, of two isomers. The mixture usually contains two isomers of less than 99.9% by weight, preferably less than 95% by weight and more particularly less than 90% by weight. Other components of the mixture may be compounds derived from the process for preparing dichloropropanol, for example residual reactants, reaction byproducts, solvents and especially water.

The mass ratio between the isomers 1,3-dichloropropan-2-ol and 2,3-dichloropropan-1-ol is usually at least 0.01, often at least 0.4, often at least 1.5, preferably at least 3.0, more preferably at least 7.0 , Very particularly preferably 20.0 or more. This ratio is usually 99 or less, preferably 25 or less.

In the process according to the invention, when chlorohydrin is dichloropropanol and is obtained by a method starting from allyl chloride, 1,3-dichloropropan-2-ol: 2,3-dichloropropan-1-ol in the isomeric mixture The mass ratio is often 0.3 to 0.6, typically about 0.5. When dichloropropanol is obtained by a method starting from synthetic and / or natural glycerol, the mass ratio of 1,3-dichloropropan-2-ol to 2,3-dichloropropan-1-ol is usually at least 1.5, preferably at least 3.0 , Especially 9.0 or more. When dichloropropanol is obtained starting from allyl alcohol, the mass ratio of 1,3-dichloropropan-2-ol: 2,3-dichloropropan-1-ol is often 0.1 times.

In the process according to the invention, when chlorohydrin is dichloropropanol, the mass ratio of 1,3-dichloropropan-2-ol to 2,3-dichloropropan-1-ol in the isomeric mixture is generally at least 0.5, often 3 Or more, often 20 or more.

In the epoxide production method according to the invention, chlorohydrin was filed on May 20, 2005 in the name of the applicant, and as described in the patent application FR 05.05120, the contents of which are incorporated herein by reference. Halogenated ketones, in particular chloroacetone. The halogenated ketone content is determined by azeotropic distillation of the chlorohydrin obtained in the process according to the present invention in the presence of water, or by treating the chlorohydrin with the dehydrochlorination treatment described in the first to sixth pages of the application. Can be reduced.

Reference is particularly made to methods of making epoxides, wherein the halogenated ketones are formed by-products and comprise one or more treatments to remove at least some of the halogenated ketones formed. One or more fractions chlorinate the polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons, or mixtures thereof, by dehydrochlorination treatment and by azeotropic distillation of the water / halogenated ketone mixture, at least of the halogenated ketones formed More particularly) and a process for preparing epichlorohydrin, wherein the halogenated ketone formed is chloroacetone.

In the epoxide production process according to the invention, chlorohydrin can be dehydrogenated to prepare epoxides as described in patent applications WO 2005/054167 and FR 05.05120 filed in the name of Solvay SA.

In the process for the preparation of the epoxide according to the invention, the epoxide is formed during the reaction of dehydrochlorination of the chlorohydrin with the basic compound.

In a first embodiment of the process for the preparation of the epoxide according to the invention, as a fraction of the reaction medium obtained in step (a), a fraction having the same composition as the reaction medium obtained in step (a) is recovered and the basic compound is recovered during the recovery. Add to the fraction.

The chlorohydrin content in this fraction is generally at least 10 μg / kg, often at least 400 g / kg, in particular at least 500 g / kg. The content is generally at most 750 g / kg, often at most 650 g / kg, in particular at most 600 g / kg.

The chlorinating agent content in the mixture fraction obtained in step (a) is generally at least 10 g / kg, often at least 20 g / kg, in particular at least 30 g / kg. The content is generally at most 150 g / kg, often at most 130 g / kg, in particular at most 100 g / kg.

The total organic acid content in the mixture fraction obtained in step (a) is generally at least 1 g / kg, often at least 2 g / kg, in particular at least 5 g / kg. The content is generally at most 40 g / kg, often at most 20 g / kg, in particular at most 10 g / kg. The total organic acid content means the total amount of organic acid itself, ester of organic acid and salt of organic acid, and this sum is expressed by organic acid itself.

In a second embodiment of the process for the preparation of the epoxide according to the invention, as a fraction of the medium obtained in step (a), a fraction having the same composition as the reaction medium obtained in step (a) is recovered and at least one separation is carried out. Treatment, for example evaporation, stripping and / or distillation, gives a portion rich in chlorohydrin and water.

The various kinds of concentrations present in this part depend in particular on the raw materials used, for example the type of chlorinating agent, the hydrogen chloride in anhydrous or aqueous solution, the water content in the polyhydroxylated aliphatic hydrocarbons or the type of organic acid used as catalyst. This can vary greatly depending on the separation or treatment. Surprisingly, the method according to the invention can be used in all such cases.

The chlorohydrin content in the chlorohydrin and water rich portions is generally at least 10 g / kg, often at least 400 g / kg, in particular at least 500 g / kg. The content is generally at most 750 g / kg, often at most 600 g / kg, in particular at most 700 g / kg.

The chlorinating agent content in this portion is generally at least 10 g / kg, often at least 20 g / kg, in particular at least 30 g / kg. The content is generally at most 150 g / kg, often at most 130 g / kg, in particular at most 100 g / kg.

The total organic acid content in this portion is generally at least 1 g / kg, often at least 2 g / kg, in particular at least 5 g / kg. The content is generally at most 40 g / kg, often at most 25 g / kg, in particular at most 100 g / kg.

In a first variant of this second embodiment, the basic compound is added to the chlorohydrin and water rich portion.

In a second variant of this second embodiment, the chlorohydrin and water-rich portion are decanted to obtain a water-rich first portion and a chlorohydrin-rich second portion.

Decantation can be carried out, for example, in a reflux reservoir of a distillation column or in any desired subsequent step, such as storage or second distillation for the purpose of purification. Devices for performing such phase separation are described, for example, in Perry's Chemical Engineers 'Handbook, Sixth Edition, Robert' H.'Perry, Don Green, 1984, sections 21-64 to 21-68.

The chlorohydrin, water and chlorinating agent contents in the two parts can be easily derived from the ternary schematic of the chlorohydrin / water / chlorinating agent mixture composition. A ternary schematic of this kind for 1,3-dichloropropanol / water / hydrogen chloride mixtures is described in G.P. Gibson, The preparation, properties, and uses of glycerol derivatives, Part III, The chlorohydrins, pages 970 to 975.

The first portion may contain chlorohydrin. The chlorohydrin content is generally at most 300 g / kg, often at most 250 g / kg, in particular at most 200 g / kg.

The chlorinating agent content in the first part is generally at least 1 g / kg, often at least 10 g / kg, in particular at least 20 g / kg. The content is generally at most 250 g / kg, often at most 200 g / kg, in particular at most 150 g / kg.

The total organic acid content in the first portion is generally at least 1 g / kg, often at least 2 g / kg, in particular at least 3 g / kg. The content is generally at most 100 g / kg, often at most 50 g / kg, in particular at most 30 g / kg.

The chlorohydrin content in the second part is generally at least 600 g / kg, often at least 700 g / kg, in particular at least 800 g / kg.

The chlorinating agent content in the second part is generally at least 1 g / kg, often at least 5 g / kg, in particular at least 10 g / kg. The content is generally at most 50 g / kg, often at most 40 g / kg, in particular at most 30 g / kg.

The organic acid content in the second part is generally at least 1 g / kg, often at least 5 g / kg, in particular at least 10 g / kg. The content is generally at most 150 g / kg, often at most 70 g / kg, in particular at most 30 g / kg.

The chlorohydrin ester content in this second portion is generally at least 1 g / kg, often at least 5 g / kg, in particular at least 10 g / kg. The content is generally at most 140 g / kg, often at most 70 g / kg, in particular at most 30 g / kg.

In a first aspect of this second variant, the basic agent is added only to the water-rich first portion.

In a second aspect of this second variant, the basic agent is added only to the second portion, which is rich in chlorohydrin.

In a third aspect of this second variant, the basic agent is added to the first portion rich in water and the second portion enriched in chlorohydrin.

In a fourth aspect of this second variant, the basic agent is added to the mixture of the first portion rich in water and the second portion enriched in chlorohydrin. The mixture may contain these two parts in various proportions. The weight ratio of the first portion rich in water to the second portion enriched in chlorohydrin is generally 1/99 to 99/1, often 89/11 to 11/89, often 81/19 to 19/81, especially 41/59 To 59/41.

The advantage of this second variant is that the composition of the part subjected to the dehydrochlorination reaction with the basic agent can be known exactly. This is because the composition of each fraction is defined by the composition of the mixture fraction obtained in step (a) comprising the conditions under which phase separation occurs, such as temperature, pressure and, in particular, chlorinating agent content, organic acid content and chlorohydrin ester content. . Knowledge of the composition of each fraction subjected to the dehydrochlorination reaction in step (c) makes it possible to control this step more effectively.

In a third embodiment of the process for the preparation of the epoxide according to the invention, as a fraction of the medium obtained in step (a), a fraction having the same composition as the reaction medium obtained in step (a) is recovered and the fraction is evaporated and stripped. Or by distillation to obtain a chlorohydrin-rich portion, and add a basic compound to this portion.

The chlorohydrin content in this portion is generally at least 100 g / kg, often at least 200 g / kg, in particular at least 400 g / kg.

The chlorinating agent content in this portion is generally at least 0.01 g / kg, often at least 0.05 g / kg, in particular at least 0.1 g / kg. The content is generally at most 110 g / kg, often at most 80 g / kg, in particular at most 65 g / kg.

The organic acid content in this portion is generally at least 0.01 g / kg, often at least 0.1 g / kg, in particular at least 1 g / kg. The content is generally at most 270 g / kg, often at most 200 g / kg, in particular at most 130 g / kg.

Evaporation is intended to indicate separation of the material by heating under appropriate reduced pressure.

Stripping is intended to denote separation by vapor-mediated incorporation from a mass in which the material is not soluble. In the process according to the invention, such agglomerates can be any desired compound which is inert to chlorohydrin, for example water vapor, air, nitrogen or carbon dioxide. Such identical compounds may constitute a gaseous stream which is optionally present in the evaporation process.

Distillation is intended to represent the condensation of the vapor obtained after the transition from the liquid state directly to the vapor state. Fractional distillation means a series of distillations that are carried out on a continuously condensed vapor. Fractional distillation is preferred.

Various embodiments may be combined with one another in any desired manner.

Basic compound means a basic organic compound or a basic inorganic compound. Basic inorganic compounds are preferred. Such basic inorganic compounds can be, for example, metal oxides, metal hydroxides and metal salts such as carbonates, hydrogen carbonates, phosphates or mixtures thereof. Among the metals, alkali metals and alkaline earth metals are preferred. Sodium, potassium and calcium and mixtures thereof are particularly preferred. The basic inorganic compound can be present in the form of a solid, liquid or aqueous or organic solution or suspension. Aqueous solutions or aqueous suspensions are preferred. Particular preference is given to solutions and suspensions of NaOH, Ca (OH) ₂ , purified alkaline brine and mixtures thereof. Purified alkaline brine means caustic soda containing NaCl of the type produced in the diaphragm electrolyte process. The amount of basic compound in solutions and suspensions is generally at least 1% by weight, preferably 4% by weight. This amount is usually up to 60% by weight. An amount of about 50% by weight is particularly suitable.

The basic compound may be used in superstoichiometric, substoichiometric or stoichiometric amounts relative to chlorohydrin. When basic compounds are used in substoichiometric amounts, usually up to 2 moles of chlorohydrin per mole of base are used. Generally, up to 1.5 moles of chlorohydrin per mole of base, preferably up to 1.05 moles of chlorohydrin per mole of base are used. If the basic agent is used in a stoichiometric amount, up to 2 moles of base per mole of chlorohydrin are used. In such cases, it is common to use at least 1.05 moles of base per mole of chlorohydrin.

The epoxide manufacturing method according to the present invention has been filed in the name of Solvay SA in the same name as the present application, the contents of which are described in the application entitled "Method for preparing epoxide starting from chlorohydrin" which is incorporated herein by reference. It can be integrated into the overall epoxide manufacturing process.

Reference is made in particular to a process for preparing an epoxide comprising at least one step of purifying the formed epoxide, wherein the epoxide is prepared at least in part through the process of dehydrochlorination of chlorohydrin, the chlorohydrin being at least partially It is prepared through the process of chlorination of polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof.

In the process according to the invention, the polyhydroxylated aliphatic hydrocarbon is preferably glycerol, the chlorohydrin is preferably dichloropropanol and the epoxide is preferably epichlorohydrin.

If the epoxide is epichlorohydrin, the epoxide can be used to prepare the epoxy resin.

1 shows a specific overview of a plant that can be used to fulfill the separation process according to the invention.

The reactor 4 is fed via line 1 with polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof, and also via catalyst 2 in a continuous or batch manner; The chlorinating agent is fed via line 3 in a continuous or batch manner; To the distillation column 6 is fed steam produced in the reactor 4 via line 5; The stream is withdrawn from column 6 via line 7 and introduced into condenser 8 and the stream from the condenser is introduced into line separator 10 separating the aqueous and organic phases via line 9. . The stream fraction from line 7 can be recovered and delivered via line 37 to the dehydrochlorination reactor 31. The basic formulation is fed to the dehydrochlorination reactor 31 via line 32. The stream containing the epoxide is withdrawn from reactor 31 via line 40. The fraction of the aqueous phase separated in the phase separator 10 is optionally recycled to the top of the column via line 11 to maintain reflux. Fresh water may be introduced into line 11 via line 12. The product of chlorohydrin is distributed between the organic phase recovered via line 14 and the aqueous phase recovered via line 13. The stream fraction from line 13 can be recovered and delivered via line 38 to dehydrochlorination reactor 31. The stream fraction from line 14 can be recovered and passed through line 39 to the dehydrochlorination reactor 31. Another portion of the stream from line 14 may be recovered and optionally passed through line 30 to the reflux of column 6. Residue from column 6 may be recycled to reactor 4 via line 15. Fractions of the heavy product are withdrawn from the reactor and introduced via line 17 to evaporator 18, and partial evaporation is carried out, for example, by heating or gas purging with nitrogen or water vapor; The gas phase comprising most of the chlorinating agent from stream 17 is recycled to column 6 via line 19 or to reactor 4 via line 20. Another fraction of the heavy product is withdrawn from reactor 4 via line 16, and a portion thereof is transferred to dehydrochlorination reactor 31 via line 34. The stream fraction from line 17 may be recovered and delivered via line 35 to the dehydrochlorination reactor 31. The stream fraction from line 21 may be recovered and delivered via line 33 to the dehydrochlorination reactor 31. Feeding the liquid phase from the stripping machine 18 to the distillation or stripping column 22 via line 21; Most of the chlorohydrin is collected at the top of column 22 via line 23 and the residue containing chlorohydrin and esters of polyhydroxylated aliphatic hydrocarbons is filtered through line 24 The liquid phase and the solid phase were separated; The liquid phase is recycled to reactor 4 via line 26. The stream fraction from line 23 may be recovered and delivered via line 36 to the dehydrochlorination reactor 31. The solid may be recovered from filtration unit 25 via line 27 in the form of a solid or solution. Solvent may be added to filtration unit 25 via lines 28 and 29 for cleaning and / or dissolution of the solid, which may be recovered via line 27.

The following examples are intended only to illustrate the invention and should not be limited thereto.

1 in practice ( according to the invention)

A mixture containing 80 g of dichloropropanol (0.62 mmol), 9.7 g of hydrogen chloride (0.27 mmol), 30 g of water and 1.3 g of acetic acid was preheated to 95 ° C. in a reactor equipped with a distillation column. Over 30 minutes, 132 g of an aqueous 280 μg / kg caustic soda solution were added thereto at a temperature of 95 ° C. and a pressure of 0.59 bar. The mixture containing epichlorohydrin and water was subsequently removed. After 20 minutes of further reaction after the addition was completed, 53.9 g of epichlorohydrin (0.58 mmol) was recovered.

2 in accordance with the invention

A mixture containing 80 g of dichloropropanol (0.62 mmol), 9.7 g of hydrogen chloride (0.27 mmol), 900 g of water and 1.3 g of acetic acid was preheated to 95 ° C. in a reactor equipped with a distillation column. Over 30 minutes, 132 g of an aqueous 280 μg / kg caustic soda solution were added thereto at a temperature of 95 ° C. and a pressure of 0.59 bar. The mixture containing epichlorohydrin and water was subsequently removed. After 40 minutes of further reaction after the addition was completed, 52.2 g of epichlorohydrin (0.56 mmol) was recovered.

Claims (25)

A reaction medium produced by reacting polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons, or mixtures thereof with a chlorinating agent, wherein the reaction medium containing at least 10 g of chlorohydrin per kg of reaction medium is subjected to no intermediate treatment. A process for producing an epoxide followed by subsequent chemical reactions. The method of claim 1, wherein the subsequent chemical reaction is a dehydrochlorination reaction. The method of claim 2, wherein the dehydrochlorination reaction is carried out by adding a basic compound to the reaction medium. (a) Reacting polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof with chlorinating agents and organic acids, esters of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons, water, chlorine Forming a chlorohydrin and chlorohydrin ester in a reaction medium containing at least 10 g of chlorohydrin per kg of reaction medium, as a reaction medium containing an agent and an organic acid, (b) at least one fraction of the reaction medium obtained in step (a), wherein the fraction having the same composition as the reaction medium obtained in step (a) is subjected to at least one treatment in a step subsequent to step (a), and (c) adding the basic compound to one or more steps subsequent to step (a) to at least partially react with chlorohydrin, chlorohydrin esters, chlorinating agents and organic acids to form epoxides and salts Method for producing an epoxide comprising a. The process according to claim 4, wherein in a subsequent step, as a fraction of the reaction medium obtained in step (a), a fraction having the same composition as the reaction medium obtained in step (a) is recovered and a basic compound is added to the fraction during recovery. . The process according to claim 4 or 5, wherein in a subsequent step, as a fraction of the reaction medium obtained in step (a), a fraction having the same composition as the reaction medium obtained in step (a) is recovered and the fraction is evaporated and / or Stripping and / or distillation to obtain chlorohydrin, chlorohydrin ester and water-rich portion, and adding the basic compound to chlorohydrin, chlorohydrin ester and water-rich portion. 7. The chlorohydrin, chlorohydrin ester and water-rich portion are decanted to obtain a water-rich first portion and a second portion rich in chlorohydrin and chlorohydrin ester, Adding to the first part, the second part or a mixture of the two parts. The method according to claim 7, wherein the mass ratio of the first portion and the second portion in the mixture is 1/99 or more and 99/1 or less. The process according to any one of claims 4 to 8, wherein in a subsequent step, as a fraction of the reaction medium obtained in step (a), a fraction having the same composition as the reaction medium obtained in step (a), and the fraction is recovered. Distillation to obtain a portion rich in chlorohydrin and chlorohydrin esters, and adding a basic compound to the portion. The method according to any one of claims 4 to 9, wherein the fraction of the reaction medium obtained in step (a) has a chlorohydrin content of at least 100 g / kg and not more than 700 g / kg, more than 1 g / kg and 200 g / kg. A chlorinating agent content of below and a total organic acid content of at least 1 g / kg and up to 500 g / kg. 7. The chlorohydrin and water-rich portion of claim 6 has a chlorohydrin content of 10 g / kg or more and 850 g / kg or less, a chlorinating agent content of 0.01 g / kg or more and 110 g / kg or less and 0.01 g / kg. And a total organic acid content of at least 270 g / kg. 8. The water-rich portion of claim 7 comprises a chlorohydrin content of 500 g / kg or less, a chlorinating agent content of more than 5 g / kg and 500 g / kg or less, and a total organic acid of 0.01 g / kg or more and 5 mol / kg or less. And a chlorohydrin rich portion containing at least 400 g / kg of chlorohydrin, from 1 ppm to 50 g / kg of chlorinating agent and from 0.0001 to 5 mol / kg of organic acid. The chlorohydrin-rich portion of claim 9, wherein the portion rich in chlorohydrin has a chlorohydrin content of at least 100 g / kg, a chlorinating agent content of greater than 0.01 g / kg and up to 110 g / kg and a total of at least 0.01 g / kg and up to 270 g / kg Method having an organic acid content. The process according to claim 1, wherein the polyhydroxylated aliphatic hydrocarbons, esters of polyhydroxylated aliphatic hydrocarbons or mixtures thereof are obtained starting from the renewable material. The method according to any one of claims 1 to 14, wherein the chlorinating agent contains hydrogen chloride. The method of claim 15, wherein the hydrogen chloride is a combination of gaseous hydrogen chloride and aqueous solution of hydrogen chloride, or the aqueous solution of hydrogen chloride. The process according to claim 4, wherein the reaction of step (a) is catalyzed by an organic acid and no organic acid is obtained during the preparation of the polyhydroxylated aliphatic hydrocarbon. 18. The process of any one of claims 4 to 17, wherein the organic acid is acetic acid or adipic acid. 19. The molar ratio of the basic compound and chlorohydrin according to claim 3, wherein the basic compound is selected from aqueous solutions or aqueous suspensions of NaOH, Ca (OH) ₂ , purified alkaline saline and mixtures thereof. Is 0.5 or more and 2 or less. The method of claim 1, wherein the polyhydroxylated aliphatic hydrocarbon is selected from ethylene glycol, propylene glycol, chloropropanediol, glycerol and mixtures of two or more thereof. The method of claim 1, wherein the chlorohydrin is selected from chloroethanol, chloropropanol, chloropropanediol, dichloropropanol and mixtures of two or more thereof. The method of claim 1, wherein the epoxide is selected from ethylene oxide, propylene oxide, glycidol, epichlorohydrin and mixtures of two or more thereof. The method of claim 20, wherein the polyhydroxylated aliphatic hydrocarbon is glycerol, the chlorohydrin is dichloropropanol and the epoxide is epichlorohydrin. The method of claim 23, wherein epichlorohydrin is used to prepare the epoxy resin. A process for producing epichlorohydrin, wherein a mixture containing dichloropropanol, hydrogen chloride and an organic acid is reacted with an aqueous solution of a basic preparation.

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